Preparation of oxygenated compounds



Sept. 6, 1938. J. E. BLUDWORTH PREPARATION OF OXYGENATED COMPOUNDS Filed Nov. 19, 1935 VENTOR JOSEPH E. BLUDWURTH mwmzmuzou m mwtss F m A u U ow or u u -L ATTORNEYS Patented Sept. s, 1938 2,128,909

UNITED STATES PATENT OFFICE PREPARATION OF OXYGENATED COM- POUNDS Joseph Elliott Bludworth, Arlington, Tern, as-

signor to Ceianese Corporation of America, a corporation of Delaware Application November 19, 1935, Serial No. 50,519

16 Claims. (Cl. 260451) This invention relates to the preparation of reactions take place. While nitrogen or low boiloxygenated compounds by processes involving ing hydrocarbons may be used as a diluent, the oxidation of hydrocarbons and relates more steam is preferred as it presents a protective inparticularly to the formation of lower aliphatic fiuence not enjoyed by other diluents.

oxygenated compounds in relatively large yields. Conveniently. he D y be ed out 5 An object of my invention is to prepare oxyby sepa ately heating a re at y a ge amount genated compounds by the oxidation of hydroof steam or other diluent to the high temperacarbons in such a manner that the nature of the tulle qu ed for the Teafition and then mixing products formed may be controlled. A further therewith the hydrocarbon to be oxygenated and object of my invention is to provide a, process the required amount of air or other oxygen-con- 10 for the oxidation of hydrocarbons wherein the mining er d r n ti ns wh reby rapid and number of oxygenated compounds formed is relthorough mixing is attained. Prior to admixture atively small and whereby such compounds may with the heated steam, the hydrocarbon and air be separated in relatively pure form from the may may not be p d, but f it is preproducts of reaction. Other objects of this inheatifi it Should be at a te pfiratu e below the 15 vention will appear from the following detailed decomposition point f. p n this mixing description. of the hydrocarbon with the heated steam, the

It has been proposed to form oxygenated oomentire mass is brought to the reaction temperapounds by the oxidation of hydrocarbons. Howtulle and Oxygenation f he hydrocarbon takes ever, in such prior processes, the number of oxyl After e O ygenation reaction is initi- 29 genated compounds formed in the reaction is ated, the sham Se ves the purpose of maintainvery large with the result that it is practically ing dilution and by ab r ing heat acts as a heat impossible to separate them into commercially dampenel' to Prevent rise of temperature to an pure components. Moreover, the yields of desired undesired eXteht- The Steam is p y as lower aliphatic compounds, such as acetaldehyde, diluent. & pe t p event excessive heat acetone, methyl alcohol, etc., have been relativegenerated by the reaction and also a substance 1 smalL I h found th t if th xid ti of used as a protective element for the products of the hydrocarbons is permitted to proceed over a y e a n. Also, the steam is used as a heat relatively large range of temperatures and for a transfer agent.

30 relatively extended period of time, secondary re- The t d g which the Oxidation reaction actions causing the formation of the large num- 18 Permitted t0 066111 Should be sufficiently o t ber of oxygenated compounds take place, SO as to inhibit the setting in Of decomposition o th th ha d, I h e found that if th reactions that tend to form undesirable prodoxygenatation process is allowed to proceed for llcts- Ordinarily the Watt-10h is pe tted to a'relatively short time under conditions whereby proceed for a Period o t0 3 ds, p e e the hydrocarbon is raised to the desired reaction ably o -5 Second. The time at which ,he temperature, large yields of lower aliphatic oxymass is permitted to remain at the p r r genated o ou d r rodu ed, th n be of of reaction is conveniently controlled by spraywhich compounds is relatively small whereby the s Otherwise injecting Water other Cooling compounds may be separated into relatively pure liquid into the reaction mass in sufiicient quantistate quite readily. Whereas, heretofore, oxidaties to quench the gases and vapors so as to retion reactions have produced a large number of duce the temperature thereof to below the dc:- compounds in small amounts, I have found that composition temperature and preferably below by varying the conditions of oxidation so that 350 F. The resulting vapors and gases are then' 4:, the reaction time is short the lower molecular conducted to a suitable system for the recovery Weight more desirable compounds are produced and separation of the oxygenated products in larger quantities. formed.

Moreover, I have found that if a large amount While I prefer to employ butane as the hydroof diluent, such as steam, nitrogen or other inert carbon to be oxygenated, other hydrocarbons such gas or vapor is present during the oxidation procas ropane, pentane, light petroleum distillate-s, ess, such diluent prevents or diminishes undesirgas oil, etc., either alone or in admixture with able reactions and formation of undesired prodeach other, may be oxygenated by this process. ucts by absorbing the heat generated during the The amount of steam, nitrogen or other gas oxidation process and thus preventing the rise of used as heat transfer agent, diluent and heat as temperature to the point where such undesired dampener is large in order to control the reaction properly, and is from 30 to 200 or more, pref erably 50 to 100, parts by gas volume per one part by gas volume of the hydrocarbon gas or vapor to be oxygenated.

The amount of oxygen employed in the reaction is also of importance in determining the nature and yields of the oxygenated product formed. For the best results, the amount of oxygen employed is that equivalent to that present in 7 to 14, preferably '1 to 10, parts by gas volume of air per one part by gas volume of the hydrocarbon gas or vapor to be oxygenated. By lncreasing the amount of diluent gas present the amount or oxygen employed may be increased. The amount of oxygen may vary between the explosive limits by a corresponding variance in amount of diluent employed.

The heating medium whether steam, air or a mixture of steam and air or other diluent should be raised to suitable temperatures, say 1,000 F. or more immediately prior to admixture with the hydrocarbon, such that when mixed with the hydrocarbon the temperature will be from 550 to 850 F. and preferably 750 to 800 F.

The hydrocarbon may be preheated prior to admixture with the air and steam, but should be preheated to a temperature below that at which decomposition tends to take place.

In order to obtain rapid heating of the hydrocarbon and consequently rapid reaction, the air and steam and the hydrocarbon are caused to approach at a high velocity to a suitable mixing device that causes mixing at high turbulence.

The reaction is preferably conducted under super-atmospheric pressures, say on the order of 25 to 500 pounds per square inch. Generally, 50 to 200 pounds per square inch pressure are suflicient to produce the desired results.

By my process, there are formed products of great commercial value and which can be separated into pure or substantially pure chemical compounds, such a acetaldehyde, formaldehyde, acetone, methyl alcohol, acetic and other organic acids as well as small proportions of methyl, propyl and butyl alcohol.

The accompanying drawing shows diagrammatically a form of apparatus that may be used in carrying out the invention.

There is provided a pipe I for introducing water into the system. Pipe I leads to a meter 9 and then to a pump 69. A pipe line 22 is provided to carry the water from the pump 69 to a quench chamber 23. The quench chamber 23 is so constructed that the products of the reaction may be cooled from the elevated temperature of reaction to about 320 F. or less.

There is a pipe 2 through which steam may be introduced into the system, which pipe may pass through a metering device 8 and into a superheater-furnace l2. The superheater furnace I2 may be provided with a coil l3 for carrying the steam therethrough. The heating coil l3 may be connected by a pipe to a mixer I3. The pipe for carrying the steam from the heating coil l3 to a mixer ll may be provided with a temperature recorder H.

A pipe or other conduit 3 may be provided for introducing air or other oxygen-containing gas into the system. Pipe 3 may pass through a meter 1 and compressor l6 into the mixer IT.

A pipe 4 may be provided for introducing butane or other hydrocarbon into the system. The pipe 4 may pass through a vaporizer 5, a metering device 6 and then to the inlet of the compressor ii. A pipe l may be provided for introducing recycle gas to the compressor It.

The course of the recycle gas will be hereinafter set forth.

At the mixer I! the air, hydrocarbon, recycle gas and steam may be admixed. The use of superheated steam produced in the superheater l2 not only aids in the heating of the mixture but also acts to maintain the same at a constant temperature. The mixture of reacting gases is led from the mixer IT to a reaction chamber It. The conduit leading from the mixer H to chamber l9 may be provided with a temperature registering device It. The reaction chamber l8 comprises a reaction zone 20 for the reacting gases. The reaction chamber l9 may be enclosed in a heater jacket. The point of initiation of reaction may be determined by the readings of thermometers 2i, a number of which are inserted at regular intervals throughout the length of the reaction zone 20. The heated and reacted gases pass from the reaction zone 20 to the quench chamber 23 where the latent heat is removed from the gases and the temperature thereof is reduced from the temperature of reaction to about 320 F. or less. In place of the furnace, shown as the reaction chamber l9, any suitable means may be employed to maintain the reaction zone 20 at a constant temperature. An alternative means may be the mere insulation of the reaction zone 20.

A pipe or conduit 24 may be provided for carrying the products of reaction from the quench chamber 23 to a cooler 25. The .temperature of the quenched reaction gases may be indicated by a temperature indicator placed in the line 24. The cooler 25 acts to control the temperature of the reaction products and to remove suflicient specific heat to follow the mixture of gases, water and other products of reaction to pass to an accumulator and absorber 28 at the proper temperature for purposes of crude distillation. A pipe or conduit 32 may be provided leaving from the absorber 28 to a still 35. Suitable temperature recording devices 26 and 30 may be inserted into the feed and discharge lines of the absorber 28. For the purpose of regulating the level of the liquids in the system a valve 3i is placed in pipe 32.

In the absorber 23 the liquid and gaseous reaction products and also the uncombined elementary gases of the mixture are separated. The liquid portion passes through the line 32 to the still 35. The gases pass out of the still by way of a pipe line 29. The liquids leaving the absorber 28 through the pipe 32 may be mixed at 33 with a very small amount 01' water previously used to absorb the product contained in the "tail" gases from the distillation system. The liquids, leaving the absorber 28 through the pipe 32, and the water injected into the system at 33 are led through a conduit or pipe 34 to the still 35, where such products of the reaction as acetaldehyde. acetone and alcohols together with some water are flashed oil. overhead. By means of suitable pipes the remainder of the liquid fraction of the reaction products, which liquid fraction comprises organic acids, formaldehyde and water, pass to a re-boller 36. The re-boiler 36 may be provided with a pipe 31 through which said boiler may be drained to waste or the liquids contained therein may be passed to further treatment. Gases liberated in the re-boiler may be returned through a suitable pipe to the bottom of the still 28.

The still 35 may be connected in any suitable manner with a dephlegmator 38 which is provided with a pipe 33 connecting it with a conamaooo denser 88. The products of the still or flash column 38 pass through the dephlegmator 88 to the final condenser 48. The condensed product from the condenser 88 may be passed by means of a pipe 4| to the crude distillate storage tank 42. The distillate in the storage tank 42 may be led to stills, not shown, for final refining.

The crude distillate storage tank 42 is connected by a pipe 43 to an absorber 44. Any vapors vented during flash distillation are led by pipe 43 to absorber N, which absorber uses an absorbent, such as water, which may be injected into the absorber by means of a pipe. .8 connecting the absorber with the supply of water I. The absorber 44 maybe connected by a pipe 81 to a recycle system into which the stripped vapors vented rrom the absorber 4! are passed. The reference numerals l8 and II indicate metering devices for measuring the quantity of water passed into absorbers 28 and N. V

The gases vented from absorber 28 are led by a pipe 29 from the absorber 28 to an oil-absorber 58 on the top of which is mounted a pipe 45 adapted to carry the stripped gases from the oil absorber out of the system. Pipe 45 may be equipped with suitable control valves and measuring devices. To the absorber 58 is also attached a pipe 5| and pipe 54, which connects the absorber 58, through an oil heater 52 and pipe 54, to a flash chamber 55. A suitable temperature indicating device 53 may be provided in this line to enable a constant temperature of oil to be maintained. The enriched absorber oil leaves absorber 58 by means of the pipe 5| and then passes to oil heater 52 where, by means of temperature indicator 53, sufficient heat is maintained to flash off in the flash chamber 55 the absorbed hydrocarbon without the need of boiling the absorber oil. A cooler 55A may be provided in the flash chamber 55 to cool the gases in the heat thereof. The gases removed from 55, after being cooled by means oi the cooler 55A, are passed through pipe 58 to a trap 84. A pipe 68, provided with a metering device 55, is adapted to connect the trap 64 with a gasometer 81. A suitable pipe I5 may be provided for connecting the gasometer 51 to the compressor IS. A suitable valve is provided to regulate the flow of recycle gases to the compressor. Metering devices are also included in this line. The gasometer 61 is employed to maintain a constant flow of gases to the intake of compressor It.

A flash chamber 55 is connected through pipe 51 with an oil cooler 58. surge tank 59. pump GI and meter 62 and through pipe 63 with the oil absorber 58 thereby forming a cyclic arrangement for the reuse of the denuded oil from flash chamber 55. A suitable reservoir 68 may be pro vided for maintaining a constant supply of oil in the system.

In dotted lines on the drawing there is shown a system wherein the oil distillation may be operated at a higher range of pressures, which system has some advantage. Instead of reducing the pressure on the oil at 5| to atmospheric conditions, a pressure is maintained in the apparatus through elements 52, 54, 55, 55, 51, 58 and 54. This pressure is lower than the pressure maintained in oil absorber 58 (but only low enough to cause the oil and gases to follow their prescribed courses). A pipe Il may be provided for connecting the trap 64 too. booster compressor 12. A by-pass 13 having a valve ll may be provided for conducting the gases around the booster compressor 12. A pipe 15 may be provided to connect the boster pump or the pipe ll to the mixer II. In this modification. the gases from trap 84 do not enter the gasometer 81 but instead pass through pipe line H and meter 18 to the booster compressor 12. Regulation of fluctuating gas flows is eilected by means or by-pass II and valve 14. The boosted" gases leave the compressor 12 by means of pipe 18 and are injected back into the system at H instead of at I! as when using the low pressure gasometer system.

In order further to illustrate my invention but without being limited thereto, the following specific example is given.

Example Butane in liquid condition and in amount equivalent to one part by volume of gas (one part by weight) is passed through the heating coil 5 where it is heated to 300 F. Water equivalent to 60 volumes of steam (18.5 parts by weight) is introduced through the pipe 2 and is heated in I! then sent to the mixer l'l where it is mixed with 10 parts by volume of air (5 parts by weight) introduced thereto by means of the pipe 3. The mixture of the three gases passes through the mixer 11 where the temperature is maintained at 550 F. The mixture of air and steam and the butane are caused to travel at high velocity to the point I! where they are mixed at high turbulence and the butane is immediately raised to the reaction temperature. This mixture is then passed to the reaction chamber is and is removed after reaction and quenched by water from the pipe 22, to below the temperature of decomposition, e. g. 300 F., the total time employed for the reaction being about .3 second.

The mixture is then introduced into the cooler 25 and absorber 28 where it is scrubbed and cooled by water introduced by pipe 21, the uncondensed gases passing out through the pressure release pipe 28, while the water and condensed oxygenated compounds leave through the pipe 32 and liquid release valve 8| to the still 35.

Owing to release of pressure in the still 35, upon the addition of suiilcient heat it necessary, oxygenated products, such as acetaldehyde, methyl alcohol, acetone, propyl and butyl alcohol, pass off as vapors through the line 88 and after condensation in the condenser 48 are collected in storage tanks 42. This mixture can be readily separated into the individual components by fractional distillation, and may then be purified by suitable chemical treatment if necessary.

The water carrying formadehyde and organic acids leave the chamber 36 by pipe 31 to storage and may be treated to recover and separate its components.

For every part by volume-or weight-butane injected at 4, about seven parts by volume of recycle gas are returned to It by line l5 alter its recovery from the vent gases leaving absorber 28 by line 28. By way of illustration, it may be stated that the gases leaving absorber 28 are made up of the following:

1.6.... CO: 16.0 CaHa and C4Hl0 8.2 CIiHG and Cal-Is 70.0 N: 3.6"... 02 1.0---- CO After leaving absorber 28 the gases (still under pressure) pass to oil-absorber 58. At this point the oil soluble constituents are absorbed from the N2, C0, C02, etc., and conducted to distillation unit 55. The gases are distilled from Per cent Per cent by volume by volume CH4 8.0 C4H1o 47.0 Cal-Is 14.63 02 1.0 CsHs 13.41 CO: 1.5 CsHs 14.0

And the vent gases may have the following constituents and about 10 volumes are vented for every volume of fresh butane injected:

Per cent by volume CO: 1.5 CO 3.8 02 2.0 N: 92.0

By way of illustration of the nature and yield of the products produced, it may be stated that for each 100 pounds of butane treated by the foregoing process, there are produced 23.0 pounds of acetaldehyde. 10 pounds of acetone, 3 pounds of methyl alcohol, 3 pounds of propyl alcohol, 3 pounds of butyl alcohol, 7 pounds of organic acids and 15 pounds of formaldehyde. The acetaldehyde may be oxidized to form acetic acid in a subsequent process.

As an example and not as an illustration, there may be used a, volume ratio of one part of butane to 10 parts of air to '70 parts of steam which has a weight ratio of 1/5/21.7. This weight of steam, 21.7 pounds, will absorb 11 B. t. u. per degree Fahrenheit. The proportion and temperature of the steam has among other functions, the functions of being a diluting or controlling agent, of acting as a heat carrier by which the heat necessary to initiate the reaction is delivered to the mixture of air and hydrocarbon under the most favorable circumstances and of a protective agent to retard decomposition of the intermediate products, particularly acetaldehyde. after they have first been formed. Other substances may replace steam for some of these functions. It is, however, preferable to use a suiiicient quantity of steam to produce all these functions,

It is to be understood that the foregoing detailed description is given merely by way of illustration and many variations may be made therein without departing from the spirit of my invention.

Having described my invention, what I desire to secure by Letters Patent is:

1. The method of producing oxygenated organic compounds, which comprises subjecting aliphatic hydrocarbons in the vapor phase to oxidation with free oxygen in the presence of at least 30 volumes of steam for each volume of hydrocarbon vapor and in the absence of oxidation catalysts.

2. The method of producing oxygenated organic compounds, which comprises subjecting aliphatic hydrocarbons in the vapor phase to oxidation with free oxygen in the presence of at least 30 volumes oi steam for each volume of hydrocarbon vapor and in the absence of oxidation catalysts, and rapidly cooling the products.

3. The method of producing oxygenated organic compounds, which comprises subjecting allphatic hydrocarbons in the vapor phase to oxidation under super-atmospheric pressure with free oxygen in the presence of at least 30 volumes of steam for each volume of hydrocarbon vapor and in the absence of oxidation catalysts.

4. Method of producing oxygenated organic compounds, which comprises subjecting aliphatic hydrocarbons in the vapor phase to oxidation under super-atmospheric pressure with free oxygen in the presence of at least 30 volumes of steam for each volume of hydrocarbon vapor and in the absence of oxidation catalysts, and rapidly cooling the products.

5. The method of producing oxygenated organic compounds, which comprises subjecting aliphatic hydrocarbons in the vapor phase to oxidation under super-atmospheric pressure with free oxygen in the presence of at least 30 volumes of steam for each volume of hydrocarbon vapor and in the absence of oxidation catalysts, rapidiy cooling the products, separating hydrocarbone from the products, and returning them to the oxidation zone.

6. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and a gas comprising iree oxygen at a temperature below that at which the hydrocarbon reacts substantially with free oxygen, with at least 30 volumes of steam for each volume of hydrocarbon vapor, the temperature of the steam being such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen.

7. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and a gas comprising free oxygen at a temperature below that at which the hydrocarbon reacts substantially with free oxygen, with at least 30 volumes of steam for each volume of hydrocarbon vapor, the temperature of the steam being such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen, and after an interval of 0.3 to 0.5 seconds rapidly cooling the mixture.

8. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and air, at a temperature below that at which the hydrocarbon reacts substantially with free oxygen and under super-atmospheric pressure, with steam in amount at least 30 times the volume of the hydrocarbon, also under pressure and at a temperature such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen, and after an interval of 0.3 to 0.5 seconds rapidly cooling the mixture.

9. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and air, at a temperature below that at which the hydrocarbon reacts substantially with free oxygen and under superatmospheric pressure, with steam in amount at least 30 times the volume of the hydrocarbon, also under pressure and at a temperature such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen, after an interval of 0.3 to 0.5 seconds rapidly cooling the mixture, separating hydrocarbons from the mixture, and returning them to the oxidation zone.

10. The method of producing oxygenated ora of steam.

ganic compounds, which comprises mixing, in the absence oi oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and air, at a temperature below that at which the hydrocarbon reacts substantially with tree oxygen and under super-atmospheric pressur with steam in amount at least 30 times the volume of the hydrocarbon, also under pressure and at a temperature such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen, and after an interval or 0.1 to 3 seconds rapidly cooling the mixture.

' 11. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of the vapor oi one or more of the lower homologues of methane and 'l to 14 volumes of air at a temperature below that at which the hydrocarbons react substantially with iree oxygen and under a pressure between and 200 pounds per square inch, with 30 to 200 volumes or steam under a similar pressure and at a temperature such that the hydrocarbons are raised to a temperature at which they react with tree oxygen, and after an interval of 0.3 to 0.5 seconds rapidly cooling the mixture.

12. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of the vapor of one or more of the lower homologues of methane and '1 to 14 volumes of air at a temperature below that at which the hydrocarbons react substantially with free oxygen and under a pressure between 50 and 200 pounds per square inch, with 30 to 200 volumes of steam under a similar pressure and at a temperature being such that the butane is raised to a temperature at which they react with free oxygen, after an interval of 0.3 to 0.5 seconds rapidly cooling the mixture, separating hydrocarbons from the mixture, and returning them in vapor iorm to the oxidation zone in amount about '7 times the volume of fresh hydrocarbon entering the zone.

13. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of butane at a temperature 01 at most about 320 F. and I to 14 volumes of air with 30 to 200 volumes all under a pressure of 20 to 500 pounds per square inch, the temperature at the steam CERTIFICATE OF CORRECTION such that the butane is raised to a temperature of 550 to 850 F., and after an interval of 0.1 to 3 seconds rapidly cooling the mixture.

14. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of butane at a temperature of at most about 320 F. and 7 to 14 volumes of air with 30 to 200 volumes of steam, all under a pressure of 20 to 500 pounds per square inch, the temperature of the steam being such that the butane is raised to a temperature of 550 to 850 F., after an interval of 0.1 to 3 seconds rapidly cooling the mixture, separating hydrocarbons from the mixture and returning them in vapor form to the oxidation zone, in amount about 7 times the volume of fresh butane entering the zone.

15. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of butane at a temperature of at most about 320 F. and 7 to 14 volumes of air, with 50 to volumes of steam, all under a pressure of 50 to 200 pounds per square inch, the temperature of the steam being such that the butane is raised to a temperature 01 750 to 800 F., after an interval of 0.1 to 3 seconds rapidly cooling the mixture, separating hydrocarbons from the mixture and returning them in vapor form to the oxidation zone, in amount about '7 times the volume of fresh butane entering the zone.

16. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and a gas comprising free oxygen at a temperature below that at which the hydrocarbon reacts substantially with free oxygen, with at least 30 volumes of steam for each volume of hydrocarbon vapor, the

bei

temperature of the steam being such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen, flashing ofi vapors and gases from the resulting products, absorbing the soluble constituents of the flashed vapors and gases in an oil, venting from the system the unabsorbed fraction of the vapors and gases, heating the oil to liberate the absorbed materials, and returning the liberated materials with fresh hydrocarbon, air and steam to the oxidation zone.

JOSEPH ELLIO'I'I BLUDWORTH.

September 6, i958- JOSEPH ELLIOTT BLUDWO RTH.

It is hereby certified that error appears in the printed specification of the above numbered. patent requiring correction as follows: Page 5, first column,

line 57, claim 12, strike out the word "being" and for "butane is" read hydrocarbons are: and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 25th day of October, A. D. 1958.

(Seal) Henry Van Aredale Acting Commissioner of Patents.

a of steam.

ganic compounds, which comprises mixing, in the absence oi oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and air, at a temperature below that at which the hydrocarbon reacts substantially with tree oxygen and under super-atmospheric pressur with steam in amount at least 30 times the volume of the hydrocarbon, also under pressure and at a temperature such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen, and after an interval or 0.1 to 3 seconds rapidly cooling the mixture.

' 11. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of the vapor oi one or more of the lower homologues of methane and 'l to 14 volumes of air at a temperature below that at which the hydrocarbons react substantially with iree oxygen and under a pressure between and 200 pounds per square inch, with 30 to 200 volumes or steam under a similar pressure and at a temperature such that the hydrocarbons are raised to a temperature at which they react with tree oxygen, and after an interval of 0.3 to 0.5 seconds rapidly cooling the mixture.

12. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of the vapor of one or more of the lower homologues of methane and '1 to 14 volumes of air at a temperature below that at which the hydrocarbons react substantially with free oxygen and under a pressure between 50 and 200 pounds per square inch, with 30 to 200 volumes of steam under a similar pressure and at a temperature being such that the butane is raised to a temperature at which they react with free oxygen, after an interval of 0.3 to 0.5 seconds rapidly cooling the mixture, separating hydrocarbons from the mixture, and returning them in vapor iorm to the oxidation zone in amount about '7 times the volume of fresh hydrocarbon entering the zone.

13. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of butane at a temperature 01 at most about 320 F. and I to 14 volumes of air with 30 to 200 volumes all under a pressure of 20 to 500 pounds per square inch, the temperature at the steam CERTIFICATE OF CORRECTION such that the butane is raised to a temperature of 550 to 850 F., and after an interval of 0.1 to 3 seconds rapidly cooling the mixture.

14. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of butane at a temperature of at most about 320 F. and 7 to 14 volumes of air with 30 to 200 volumes of steam, all under a pressure of 20 to 500 pounds per square inch, the temperature of the steam being such that the butane is raised to a temperature of 550 to 850 F., after an interval of 0.1 to 3 seconds rapidly cooling the mixture, separating hydrocarbons from the mixture and returning them in vapor form to the oxidation zone, in amount about 7 times the volume of fresh butane entering the zone.

15. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, one volume of butane at a temperature of at most about 320 F. and 7 to 14 volumes of air, with 50 to volumes of steam, all under a pressure of 50 to 200 pounds per square inch, the temperature of the steam being such that the butane is raised to a temperature 01 750 to 800 F., after an interval of 0.1 to 3 seconds rapidly cooling the mixture, separating hydrocarbons from the mixture and returning them in vapor form to the oxidation zone, in amount about '7 times the volume of fresh butane entering the zone.

16. The method of producing oxygenated organic compounds, which comprises mixing, in the absence of oxidation catalysts, an aliphatic hydrocarbon in the vapor phase and a gas comprising free oxygen at a temperature below that at which the hydrocarbon reacts substantially with free oxygen, with at least 30 volumes of steam for each volume of hydrocarbon vapor, the

bei

temperature of the steam being such that the hydrocarbon is raised to a temperature at which it reacts with free oxygen, flashing ofi vapors and gases from the resulting products, absorbing the soluble constituents of the flashed vapors and gases in an oil, venting from the system the unabsorbed fraction of the vapors and gases, heating the oil to liberate the absorbed materials, and returning the liberated materials with fresh hydrocarbon, air and steam to the oxidation zone.

JOSEPH ELLIO'I'I BLUDWORTH.

September 6, i958- JOSEPH ELLIOTT BLUDWO RTH.

It is hereby certified that error appears in the printed specification of the above numbered. patent requiring correction as follows: Page 5, first column,

line 57, claim 12, strike out the word "being" and for "butane is" read hydrocarbons are: and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 25th day of October, A. D. 1958.

(Seal) Henry Van Aredale Acting Commissioner of Patents. 

